Article
A Cationic Unsaturated Platinum(II) Complex that Promotes the Tautomerization of Acetylene to Vinylidene
Author/s | Ortega Moreno, Laura
Peloso, Riccardo López Serrano, Joaquín Iglesias Sigüenza, Francisco Javier Maya Díaz, Celia María Carmona Guzmán, Ernesto |
Department | Universidad de Sevilla. Departamento de Química Inorgánica |
Publication Date | 2017 |
Deposit Date | 2018-05-30 |
Published in |
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Abstract | Complex [PtMe(PMeAr)] (1), which contains a tethered terphenyl phosphine (Ar =2,6-(2,6-PrCH)CH), reacts with [H(EtO)]BAr (BAr =B[3,5-(CF)CH] ) to give the solvent (S) complex [PtMe(S)(PMeAr)] (2⋅S). Although the solvent ... Complex [PtMe(PMeAr)] (1), which contains a tethered terphenyl phosphine (Ar =2,6-(2,6-PrCH)CH), reacts with [H(EtO)]BAr (BAr =B[3,5-(CF)CH] ) to give the solvent (S) complex [PtMe(S)(PMeAr)] (2⋅S). Although the solvent molecule is easily displaced by a Lewis base (e.g., CO or CH) to afford the corresponding adducts, treatment of 2⋅S with CH yielded instead the allyl complex [Pt(η-CH)(PMeAr)] (6) via the alkyne intermediate [PtMe(η-CH)(PMeAr )] (5). Deuteration experiments with CD, and kinetic and theoretical investigations demonstrated that the conversion of 5 into 6 involves a Pt-promoted HC≡CH to :C=CH tautomerization in preference over acetylene migratory insertion into the Pt−Me bond. |
Citation | Ortega-Moreno, L., Peloso, R., López-Serrano, J., Iglesias Sigüenza, F.J., Maya, C. y Carmona, E. (2017). A Cationic Unsaturated Platinum(II) Complex that Promotes the Tautomerization of Acetylene to Vinylidene. Angewandte Chemie International Edition, 56 (10), 2772-2775. |
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